Unsaturated dioxolane compounds, products prepared therefrom, and methods of preparation



Patented Dec. 18, 1951 UNSATURATED DIOXOLANE COMPOUNDS. PRODUCTS PREPARED THEBEEROM, AND METHODS OF PREPARATION Walter M. Thomas, Springdale, and Edward L. Kropa, Old Greenwich, Conn., assignors to American Cyanamid Company, New York, N. Y., a corporation of Maine No Drawing. Application July 26, 1949, Serial No. 106,974

21 Claims. (01. 260-855) 1 This invention relates to new unsaturated dioxolane compounds, to polymerization products prepared therefrom and to methods of preparing the said compounds and products. More particularly the invention is concerned with compounds represented by the general formula where R represents an allyloxymethyl radical, and R represents a monovalent hydrocarbon radical, more particularly an aryl radical, and with the production of polymers (homopolymers) and copolymers (or interpolymers) therefrom. The scope of the invention includes polymerizable compositions comprising (1) an unsaturated dioxolane of the kind embraced by Formula I and (2) a compound which is different from the compound of (1), is copolymerizable therewith and which contains a CHz=C grouping, as well as compositions comprising a copolymer of copolymerizable ingredients including as essential components the aforementioned compounds of .(1) and (2).

Illustrative examples of radicals which R can represent, including examples of aryl radicals, are the following: aliphatic (both saturated and unsaturated) hydrocarbon radicals (e. g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec.-butyl, tert.-butyl, amyl, isoamyl, hexyl, octyl, decyl, dodecyl, octadecyl, allyl, methallyl, ethallyl, propallyl, 2-butenyl, 3-butenyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 2-pentenyl, 4-pentenyl, 2- methyl-Z-pentenyl, 3-methyl-4-pentenyl, 2-hexenyl, 2,3-pentadienyl, 2,4-hexadienyl, 2-octenyl, 3-nonenyl, z -decenyl, etc.), including cycloaliphatic (e. g., cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, etc.) aromaticsubstituted aliphatic hydrocarbon radicals (e. g., benzyl, phenylethyl, phenylpropyl, phenylisopropyl, cinnamyl, phenylallyl, etc.) aromatic hydrocarbon radicals (e. g., phenyl, biphenylyl, naphthyl, etc.); and aliphatic-substituted aromatic hydrocarbon radicals e. g., tolyl, xylyl, ethylphenyl, propylphenyl, isopropylphenyl, butylphenyl, vinylpheny'l, allylphenyl, z-butenylphenyl, etc.).

Illustrative examples of compounds embraced by Formula I are:

4-allyloxymethyl-2-crotyl-1,3-dioxolane 4-allyloxymethyl-2-tolyl--1,3-dioxolane The new compounds of this invention embraced by Formula I can be prepared, for example, by effecting reaction under heat, while admixed 2 with a small amount of a strong acid (e. 3., sulfuric acid, phosphoric acid, etc.) as a catalyst for the reaction, between (1) a dihydric alcohol represented by the formula 5 n R-cn-cm H on where R has the same meaning as given above, and (2) an aldehyde represented by the formula RCHO, where R likewise has the same meaning as given above, and thereafter isolating a compound represented by the first-mentioned formula from the resulting reaction mass.

When R in Formula I represents a hydrogen l5 atom, the formula embraces 4-allyloxymethyl- Lil-dioxolane. When R in Formula I represents a hydrogen atom and R represents either a vinyl or an allyl radical, the formula covers either 4-vinyl-1,3-dioxolane or 4-allyl-1,3-di- 2o oxolane, depending upon the meaning of R. When R in Formula I represents a monovalent hydrocarbon radical, specifically a phenyl radical, and R represents, for example, a vinyl radical, the formula covers 4-vinyl-2-phenyl-L3-dioxolane. Included in the specification of the present application are specific examples showing the preparation of monomeric 4-vinyl-L3- dioxolane (Example 1), 4-vinyl-2-phenyl-L3-dioxolane (Example 2), 4-allyloxymethyl-L3-dioxolane (Example 3) and 4-al1yl-1,3-dioxolane (Example 5), as well as examples showing the production of homopolymers and various copolymers from such unsaturated dioxolanes.

Many difierent vinyl and allyl compounds were known prior to our invention, but to the best of our knowledge and belief compounds of the kind embraced by Formula I heretofore have been unknown. These compounds are unique in that they can be caused to polymerize either through the ethylenically unsaturated bond of the compound or through both the unsaturated linkage and the dioxolane ring. By suitable choice of catalysts, polymerization can be caused to take place primarily through the ring. Because of their unique structure and properties, the plastics chemist and resin formulator, and workers, in related arts are now' provided with a single polymerizable material which, alone or admixed with another comonomer, can be caused to undergo either or both of two types of polymerization reactions as briefly described above. The advantages of such a polymerizable compound will be apparent to those skilled in the art, for example. the greater adaptability of such compounds for a greater variety of service applications by merely varying the catalyst or other polymerization influences employed, or the temperature or other polymerization conditions used, so as to direct the course of the polymerization through the ethylenic linkage and/or the dioxolane grouping as desired or as conditions may require.

The unsaturated dioxolanes of, this invention can be caused to polymerize alone or while admixed with one or more (e. g., two, three, five, ten, or any desired number) of other comonomers which are copolymerizable therewith, more particularly such comonomers which contain a CH2=C grouping (that is, comonomers which contain either a single CH2=C grouping or a plurality of such groupings), thereby to obtain homopolymers and copolymers, which in general are resinous or potentially resinous materials and which are especially valuable for use in the plastics, coating, laminating, adhesive, molding and other arts. Examples of comonomers with which our new unsaturated dioxolanes can be copolymerized are vinyl compounds, more particularly vinyl aromatic compounds (e. g., styrene, dimethyl styrene, divinyl benzene and other vinyl aromatic hydrocarbons) and vinyl aliphatic compounds, for instance acrylonitrile, acrylamide, the alkyl esters of acrylic acid (e. g., methyl, ethyl, propyl, etc., acrylates), the various allyl esters, e. g., allyl acetate, diallyl phthalate, diallyl succinate, etc.

It is an object of the present invention to provide a new class of polymerizable monomers. more particularly a new class of unsaturated dioxolanes of the kind embraced by Formula I.

Another object of the present invention is to provide a new class of polymerizable compositions containing a compound of the kind embraced by Formula I (or a plurality of such compounds) and one or more other comonomers copolymerizable therewith, and a new class of copolymer compositions from the said polymerizable compositions.

Another object of the invention is to provide a new class of synthetic compositions, more particularly resinous polymers and copolymers, which are especially suitable for use in the plastics, coating, adhesive, laminating, molding and other arts.

Other objects of the invention will be apparent to those skilled in the art from the following more detailed description thereof.

The foregoing objects are attained by preparing chemical compounds of the kind embraced.

by Formula I and then polymerizing such a compound either alone, or while admixed with each other, or while one or more of such compounds are admixed with one or more other comonomers which are different from monomers of the kind shown generically in Formula I and which are copolymerizable therewith, more particularly such comonomers which contain either a single or a plurality of CH2=C groupings.

The preparation of the new monomers of this invention by one suitable method is illustrated by the following equation:

In R-cn-cn, n'cno strong acidic ably using a slight molar excess (e. g., from 5 to 20 mole percent in excess) of the latter, are mixed with a small amount of a strongly acidic substance, e. g., a strong acid, as a catalyst for the reaction, e. g., sulfuric acid, phosphoric acid, p-toluene sulfonic acid, aluminum chloride, ferric chloride, etc. The reaction vessel containing the resulting mixture is heated, while stirring the mixture, in a bath maintained at about 150 C. The aldehyde may be anhydrous, or it may be in the form of an aqueous solution. e. g., formalin. The acidic catalyst is employed in an amount suflicient to catalyze the reaction, for instance about 0.5 to 5 by weight of the total amount of dihydric alcohol and aldehyde (calculated as anhydrous aldehyde) used. After a reaction period of about 1 hour, the reaction mass is cooled and thereafter is preferably washed with water or aqueous alkali solution to remove the acidic catalyst and unreacted glycol. The washing step may be omitted, but there is then the greater possibility of charring the reaction product or even of explosive decomposition of the same when the mass is subsequently heated during distillation. The unsaturated dioxolane is recovered as a distillate by vacuum distillation of the crude reaction product, or by extraction with a suitable solvent.

In producing the polymerization products of our invention, the unsaturated dioxolane can be polymerized alone but it is preferably polymerized while admixed with a comonomer (or a plurality of comonomers) containing one or more CH2=C groupings since, in general, products having optimum properties for a particular service use thereby can be obtained at minimum cost. Heat, light or heat and light can be used to effect polymerization, although under such conditions the rate of polymerization is relatively slow. Hence, to accelerate the polymerization, we prefer to use a polymerization catalyst accompanied by heat, light or heat and light. Further details on polymerization conditions are given hereinafter.

Examples of monomers containing a CH2=C grouping that can be copolymerized with one or more unsaturated dioxolanes of the kind embraced by Formula I, either singly or a plurality (two, three, four or any desired number) thereof, the latter often being desirable in order to improve the compatibility and copolymerization characteristics of the mixture of monomers and to obtain new and valuable copolymers having the particu lar properties desired for a particular service application, are such monomers as the unsaturated alcohol esters, more particularly the allyl,

methallyl, crotyl, l-chloroallyl, 2-chloroallyl, cinnamyl, vinyl, methvinyl, l-phenylallyl, butenyl, etc., esters of saturated and unsaturated, aliphatic and aromatic, monobasic and polybasic acids such, for instance, as acetic, propionic, butyric, valeric, caproic, acrylic and alpha-substituted acrylic (including alkacrylic, e. g., methacrylic, ethacrylic, propacrylic, etc., and arylacrylic, e. g., phenylacrylic, etc.), crotonic, oxalic, malonic, succinic; glutaric, adipic, pimelic, suberic, azelaic, sebacic, maleic, fumaric, citraconic, mesaconic, itaconic, acetylene dicarboxylic, aconitic, benzoic, phenylacetic, phthalic, terephthalic, benzoylphthalic, etc., acids; the saturated monohydric alcohol esters, e. g., the methyl, ethyl, propyl, isopropyl, butyl, sec.-butyl, amyl, etc., esters of unsaturated aliphatic monobasic and polybasic acids, illustrative examples of which appear abov vinyl cyclic compounds (including monovinyl arobenzene, trivinyl benzene, allyl benzene, diallyl benzene, N-vinyl carbazole, the various allyl cyanostyrenes, the various alpha-substituted styrenes and alpha-substituted ring-substituted styrenes, e. g., alpha-methyl styrene, alphamethyl-paramethyl styrene, etc.; unsaturated ethers, e. g., ethyl vinyl ether, diallyl ether, ethylmethallyl ether, etc.; unsaturated amides, for instance N-allyl caprolactam, acrylamide, and N-substituted acrylamides, e. g., N-methylol acrylamide, N-allyl acrylamide, N-methyl acrylamide,

butadiene, 2-chlorobutadiene, etc.; unsaturated polyhydric alcohol (e. g., butenediol, etc.) esters 'of saturated'and unsaturated, aliphatic and aromatic, monobasic and polybasic acids, illustrative examples of which appear above.

Other examples of monomers that can be copolymerized with the compounds embraced by Formula I are the vinyl halides, more particularly vinyl fluoride, vinyl chloride, vinyl bromide and vinyl iodide, and the various vlnylidene compounds, including the vlnylidene halides, e. g.,

vlnylidene chloride, vinylidene bromide, vlnylidene fluoride and vlnylidene iodide, other comonomers being added if needed in order to improve the compatibility and copolymerization characteris- Other and more specific examples of monomeric materials which may be mixed or blended with the unsaturated dioxolanes used in practicing our invention and the resulting homogeneous or substantially homogeneous, polymeri'zable composition then polymerized, as hereinafter more fully described, to yield new and valuable copolymer' compositions are the allyl compounds which are diiierent from those allyl compounds embraced by Formula I and especially those which have a boiling point of at least about 0. or the monomeric materials which may be used the allyl esters form a large class, all of which are suitable. The reactive allyl compounds employed are preferably those which have a high boiling point such, for example, as diallyl maleate, diallyl 55 iumarate, diallyl phthalate, diallyl succinate, etc. Other allyl compounds which are not necessarily high boiling also may be used.

More specific examples of allyl compounds that can be copolymerized with compounds of the kind nate, the diallyl ester of muconic acid, diallyl 70 Tert buty1 perbenzoabe itaconate, diallyl chlorophthalate, diallyl dichlorosilane, the diallyl ester of endomethylene tetrahydrophthalic anhydride, triallyl tricarballylate, triallyl aconitate, triallyl cyanurate, triallyl citrate, triallyl phosphate, trimethallyi phosphate, (5

6 tetrallyl silane, tetrallyl silicate, hexallyl disiloxane, etc. Other examples oi allyl compounds that may be employed are given, for example, in the copending application of Edward L. Kropa. Serial No. 700,833, filed October 2, 1946, now Patent No. 2,510,503, issued June 6, 1950.

Among the comonomers which are preferred for use in carrying our invention into effect are the vinyl compounds, including the vinyl aromatic compounds, more particularly the vinyl aromatic hydrocarbons (e. g., styrene, isopropenyl toluene, the various dialkyl styrenes, etc.), and the vinyl aliphatic compounds, e. g., acrylonitrile, acrylamide, etc., and other compounds containing a CH2=C grouping, e. g., the various substituted acrylonitriles (e. g., methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, etc.) the various substituted acrylamides (e. g., methacrylamide,

ethacrylamide, the various N-substituted acrylamides and alkacrylamides, for instance N-methylol acrylamide, N-monoalkyl and -dialkyl acrylamides and methacrylamides, e. g., N-monomethyl, -ethyl, -propyl, -butyl, etc., and N-dimethyl, -ethyl, -propyl, -butyl, etc., acrylamides and methacryla-mides, N-monoaryl and -diaryl acrylamides and alkacrylamides, e. g., N-monophenyl and -diphenyl acrylamides and methacrylamides, etc.) vinyl esters, e. g., vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl valerate, vinyl acrylate, vinyl methacrylate, etc.. esters of an acrylic acid (including acrylic acid itself and the various alpha-substituted acrylic acids, e. g., methacrylic acid, ethacrylic acid, phenylacryllc acid, etc.), more particularly the alkyl esters of an acrylic acid, e. g., the methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl. sec.-butyl, tert.-butyl, amyl, hexyl, heptyl, octyl, decyl, dodecyl, etc., esters of acrylic, methacrylic,

' ethacrylic, phenylacryllc, etc., acids, including tics of the mixed monomers. 40

the alkyl acrylates containing not more than four carbon atoms in the ester grouping, examples of which are given above, as well as other vinyl aromatic and vinyl aliphatic compounds, and other compounds containing a CH2=C grouping.

Any suitable means may be used in effecting polymerization of the unsaturated dioxolane embraced by Formula I, either alone or admixed with one another, or admixed with one or more other monomers which are copolymerizable therewith. Heat or light or both,with or without a polymerization catalyst, can be used. Ultraviolet light is more effective than ordinary light. Preferably a polymerization catalyst is employed. Any of the catalysts which are useful in accelerating the polymerization of compounds containing an ethylenically unsaturated grouping, specifically a vinyl grouping, can be used. Among the preferred catalysts are: the acidic peroxides,

e, g., benzoyl peroxide, phtalic peroxide, succinic peroxide and benzoyl acetic peroxide, as well as fatty oil acid peroxides, e. g., coconut oil acid peroxides, lauric peroxide, stearic peroxide and oleic peroxide; alcoholic peroxides, .e. g., tert.-butyl hydroperoxide; and terpene oxides, e. g., ascaridole. Other examples of organic peroxide catalysts that can be employed are the following;

Tetralin hydroperoxide Tert.-butyl diperphthalate Cumene hydroperoxide Acetyl peroxide 2,4-dichlorobenzoyl peroxide Urea peroxide Caprylyl peroxide p-Chlorobenzoyl peroxide 2,2-bis(di-tert.-butyl peroxy) butane Hydroxyheptyl peroxide Diperoxide of benzaldehyde Examples of catalysts which are believed to accelerate polymerization primarily by opening up the dioxolane ring and, also, may cause polymerization to proceed through the ethylenically unsaturated grouping are: p-toluene sulfonic acid, sulfuric acid, phosphoric acid, aluminum chloride,

stannic chloride, ferric chloride, boron trifiuoride-ethyl ether complex, iodine, etc. Certain alkaline catalysts also seem to function in a similar manner, e. g., ethylene diamine, tetraethylenepentamine, etc.

Catalysts which accelerate polymerization as the result of the liberation of a free radical, e. g., sym-dicyanotetramethylazomethane and similar known diazo polymerization catalysts, also can be employed.

If desired, partial polymerization of the unsaturated dioxolane can be effected with the aid of one polymerization catalyst (e. g., a peroxide and, more particularly, an organic peroxide catalyst, or with a diazo or other type of catalyst capable of liberating a free radical) and polymerization then completed with the aid of a catalyst capable of opening up the dioxolane ring, e. g., stannic chloride, etc. v

The concentration of catalyst is relatively small, e. g., from, by weight, about 1 part of catalyst per thousand parts of the monomer or mixture of monomers to be polymerized to about 3 or 4 or more parts of catalyst per hundred parts of the monomer or mixture of monomers. If an inhibitor be present in the polymerizable composition, up to 6 or 7% or even more, based on the weight of the said composition, may be necessary (according to the concentration of the inhibitor) in order to overcome the effect of the inhibitor and to cause polymerization to proceed as desired within a reasonable period of time.

The proportions of the unsaturated dioxolane and monomeric material which is copolymerlzed therewith may be varied as desired or as conditions may require, but ordinarily the proportions thereof in the polymerizable mixture will be within the range of, by weight, from 3 (about 3) to 97 (about 97), or higher, molar percent of the unsaturated dioxolane to from 97 (about 97) to 3 (about 3), or lower, molar percent of the other comonomer. Preferably the unsaturated dioxolane constitutes at least molar percent of the mixture thereof with the other comonomer or mixture of comonomers. monomer constitutes only about 3 molar percent by weight of the polymerizable composition and the unsaturated dioxolane constitutes the remainder, the changes in the properties of the polymerization product are less marked (as compared with the homopolymeric dioxolane) than when the comonomer (or mixture of comonomers) constitutes a substantially larger amount, as for example 10 or 20 molar percent or even as much as 30 or 40 molar percent of the polymerizable composition. Particularly valuable copolymer compositions are obtained by using, by weight, from 50 to 90 molar percent of the unsaturated dioxolane and from 10 to 50 molar percent of a comonomer (or mixture of comonomers) which is copolymerizable therewith and which contains a CH2=C grouping, numerous examples of which have been given hereinbefore.

In some cases it may be desirable to incorporate into the polymerizable composition (especially those comprising the unsaturated dioxo- When the colane and one or more comonomers) an inhibitor which is adapted to inhibit polymerization through the ethylenically unsaturated grouping oi the monomeric material. When it is desired to use the inhibitor-modified composition, a catalyst is added in an amount suillcient to promote the polymerization reaction. Various inhibitors can be used for this purpose, e. g., nhenyl-a-naphthylamine, N,N'-di-2-naphthylp-phenylenediamine, certain cupric salts, e. g., cupric acetate, etc. The amount of inhibitor may be considerably varied but ordinarily it is employed in an amount not exceeding 3%. enerally less than 1%, by weight of the polymerizable composition, e. g., from 0.01% to 0.5% or 0.6% by weight of the said composition.

The polymerization may be effected by conventional bulk polymerization technique, in the presence or absence of a solvent capable of dissolving the monomer (or mixture of monomers) and in which the latter preferably is inert; or

by conventional emulsion polymerization or bead polymerization methods. Polymerization of the monomer or mixture of monomers may be effected by a continuous process as well as by a batch operation. Thus, the unsaturated dioxolane or mixture thereof with one or more other comonomers, to which has been added a small amount of a suitable polymerization catalyst, may be caused to polymerize to yield a homopolymer or interpolymer by passage through a conduit with alternate hot and cool zones.

The temperature of polymerization of the polymerizable composition, at atmospheric or slightly above atmospheric pressure and in the presence or absence of a polymerization catalyst,

,may be varied over a wide range, up to and including or slightly above the boiling point at atmospheric pressure of the monomer or mixture of monomers. In most cases the polymerization temperature will be within. the range of 15 to 200 C., more particularly within the range of 20 C. or 30 C. (ordinary room temperature) to l30--140 0., depending, for example, upon the rapidity of polymerization (or copolymerization) wanted, the particular catalyst, if any, used, the particular mixture of comonomers employed when a particular copolymer is wanted, and other influencing factors. With certain polymerization catalysts, more particularly strong acidic polymerization catalysts such, for instance, as gaseous boron trifluoride, boron trifluoride-ethyl ether complex, concentrated sulfuric acid, anhydrous aluminum chloride, etc., a substantially lower polymerization temperature often advantageously can be used, e. g., temperatures ranging between 80 C. and 0 or 10 C. At the lower temperatures below the solidificationpoint of the monomeric composition, polymerization of the said composition is effected while it is dissolved or dispersed in a solvent or dispersion medium which is liquid at the polymerization temperature. Or, if desired, the monomeric composition may be polymerized in dissolved or dispersed state at temperatures above its solidification point or above the solidification point of copolymerizable components thereof. The polymerization product may be separated from the liquid medium in which polymerization (or copolymerization) was effected by any suitable means, e. g., by filtration, centrifuging, solvent extraction, etc.

The polymerizable compositions of our invention which are normally liquids may be cast at normal temperatures in film or bulk form. Upon 9 1 being subjected to polymerization conditions above described, hard films or massive castings are obtained. 1 r g In order that those skilled in the art better may understand how the present invention can be carried into eifect. the following examples are given by way of illustration and not by way of limitation. All parts and percentages are by weight.

Example 1 This example illustrates the preparation of 4- vinyl-1,3-dioxolane, the formula for which is Parts 3,4-dihydroxy-1-butene 70 Aqueous solution of formaldehyde (approx.

37% HCHO) 90 Phosphoric acid (approx. 85% H3PO4) 6 Example 2 This example illustrates the preparation of 4-vinyl-2-phenyl-1,8-dioxolane, the formula for which is v Approx. Molar Ratios Parts 3,4-Dih droxy-l-butene 0 l. Behzal ehyde .Q 117.0 1. Phosphoric acid (approx. 85% HIPO) 0 are heated together for 1 hour in a reaction vessel placed in a 150' C. oil bath. Thereafter the vessel is cooled and the contents are shaken twice with water in a separatory funnel. The oil layer is ,dried over sodium sulfate, filtered and distilled under vacuum. Distillation yields 4-viny1-2- phenyl-1,3-dioxolane, boiling at 102-105 C. at 4 mm. pressure, in a yield of approximately Example 3 This example illustrates the preparation of 4-allyloxymethyl-L3-dioxolane, the formula for which is are heated together under reflux in a reaction Ap rox. Parts olar Ratios Glycerol-wally] ether 132. 0 1. 0 Aqueous solution oi formaldehyde (approx. 37% H 00.0 1.1 Phosphori acid (approx. H;P04) 6.0

A mixture ofthe above ingredients is heated under reflux at the boiling temperature of the mass for 1% hours. After distilling of! the water and excess formaldehyde from the resulting reaction mass,-the residue is neutralized with triethanolamine and thereafter washed with water. Distillation is continued until no more distillate is obtained at a bath temperature of 175 C. The distillate is shaken with CaCla and redistilled under reduced pressure. 4-allyloxymethyl-L3- dioxolane is collected as the product boiling at 82-85 C. under a pressure of 15 mm. in a yield amount to about 29%. It is a clear, mobile, colorless liquid; a 1.4401.'

Example 4 This example illustrates the preparation of 4 allyloxymethyl 2 -phenyll,3-dioxolane, the formula for which is Parts Molar ether 1. 0 l. l

vessel placed in an oil bath having an initial temperature of C. and rising to 150 C. within 40 minutes. Heating is continued for 1 hour at a bath temperature of -150 C. The resulting reaction mass is washed twice with water in a separatory funnel followed by drying over sodium sulfate, and is then distilled under reduced pressure. After removing a fore-run of'water and benzaldehyde, 4-allyloxymethyl-2-phenyl-1,3-dioxolane, boiling at 138 C. under a pressure of 3-4 mm., is obtained in a yield of approximately 24%. It is a water-white, slightly viscous liquid.

Example 5 x This example illustrates the preparation of 4-. a11yl-1.3-dioxolane, the formula for which is VIII CH:=CHCH:CH- CH| Approx. Parts Molar Ratios 5-Dihydroxy-1-pentene 102. 0 l. 0 kqueous solution of formaldehyde (approx.

37% HCHO) 90.0 1. 1 Sulfuric acid (95%) 5.5

A mixture of the above ingredients is stirred for two hours in a reaction vessel placed on a steam bath, cooled, transferred to a separatory funnel and shaken with a dilute aqueous solu- 12 tion of sodium bicarbonate. The layers are septions. For example; it may be applied to a surarated, and the non-aqueous layer is distilled unface of glass, metal, wood or other material to be vder reduced pressure to isolate 4-allyl-1,3-dioxoprotectively finished, and the coated article then lane. heated for from 1 to 3 hours at a temperature Example 6 5 of the order of 120 C. to 140 C. to evaporate the water and to convert the reactive styrene- Pal'ts unsaturated dioxolane copolymer to a cured or 4-a1lyloxymethy1-L -dioxolane substantially insoluble, substantially infusible Ethyl acry state.

Benzene 209 10 The copolymer may be precipitated, if desired. Benzoyl peroxide from the aqueous emulsion thereof by adding a e heated to ether under reflux at the boilin coagulating agent such for instance as Salts temperature 0% the mass for 5 hours. The result- Salts POlyvalent metals Such as alumiing viscous solution containing a copolymer of num sulfate, magnesium chloride, barium ch10- ethyl acrylate and the aforementioned dioxolane 5 ride, etc., salts of monovalent metals such as sois cooled, and the content of copolymer solids is chmnde' sdium sulfate, etcJv F S determined by oven drying for 2 hours at formic acid, acetic acid, phosphoric acid, hydro- The ylld of copolymer solids is 365%, which chloric acid, etc., sulfides, e. g., magnesium sulcorresponds to 73.2% conversion of monomers to tide The wagulated 1S Separated copolymer. Films dried from the benzene solufrom the 11180115 Phase, Water-Washed. and tion of the copolymer are clear and tough. The freed fmm entrapped Waterfor example by copolymer of this example is suitable for use as working on rolls to press out the water, followed a component of coating compositions by drying at a suitable temperature (e. g., at

Instead of ethyl acrylate other comonomers, room temperature) under atmospheric pressure more particularly other esters of acrylic acid. 5 (preferably in a stream of dry air) or at sube g. methyl acrylate propyl acrylate, isopropyl atmospheric pressures to remove the last traces acrylate mbutYl acrylate isobutyl acrylate of water. The dried, reactive copolymer, alone butyl acrylate, tert.-butyl acrylate, amyl acrylate, r with a dye, pigment, flller, plasticizer, lubrihexyl acrylate propenyl acrylate, cyclohexyl cant, polymerization catalyst or other modlfyll'lg acrylate, phenyl acrylate, benzyl acrylate, etc., agent may m1dedunder heat and Pressurecan be substituted in the above formulation to 170 and under a pressure thereby to obtain copolymer compositions of of 20 to 00 pounds square inchvarying properties. As with ethyl acrylate. so Example 10 too with such other comonomers the proportions of components can be varied as desired or as Same as inExample 9 with the exception that conditions may require 6 g from 3 to 97 (or 20 parts of 4-allyl-1,3-dioxolane is used in place higher) m of percent b g dioxolane to from of 20 parts of 4-vinyl-1,3-dioxolane. Similar re- 97 to 3 (or lower) molar percent of the other sun's are obtained comonomer. Preferably the comonomer consti- 40 Example 11 tutes from to 95-90 molar Pement of the Same as in Example 9 with the exception that mixture thereof with the noxolane' 20 parts of -allyloxymethyl-1,3-dioxolane is Example 7 employed instead of 20 parts of 4-vinyl-1,3-disame as m n 6 with the exception that oxolane. Similar results are obtained.

10 parts of 4-vinyl-l,3-dioxolane is used in place Example-12 of 10 parts of 4-ally1oxymethyl-L3-dioxolane. Parts Similar results are obtained. Acrylonitrile 25,0 Example 8 4-a11yloxymethyl-1,3-dioxo1ane 25.0 Benzene 50.0 Same as in Example 6 with the exception that Benzoyl peroxide 0.5

10 parts of 4-allyl-l,3-dioxolane is employed in place of 10 parts of 4-allyloxymethyl-1,3-dioxoare heated together under reflux at the boiling 181m similar results are t temperature of the mass for 5 hours. From the resulting mass a solid copolymer of acrylonitrile l P 9 and 4-allyloxymethyl-1,3-dioxolane can be iso- Parts' lated by evaporating or distilling off the benzene. Styrene 180.0 Example 13 4-vinyl-l,3-dioxolane 20.0 Parts 25% solution of dioctyl sodium sulfosucstyrene 190 cmate in Water m 4-vinyl-1,3-dioxolane 10 water 580-0 Benzoyl peroxide l Ammonium persulfate 0.1

yield a clear, viscous copolymer when heated toare charged to a 3-necked reaction vessel gether for 48 hours at 100 C.

equipped with a stirrer and a reflux condenser. 5

The mixture is stirred vigorously while heating Example 14 on a steam bath for 90 minutes, at the end of Parts which period refluxing has ceased. Steam is now Ethyl acrylate 90 passed through the emulsion for 15 minutes to '4'vmyl'l'a'dioxolane 10 remove residual monomers. A small amount of 7 are di lv d t t d t resulting Solucoagulated copolymer is filtered out-of the stable tion is then added to emulsion of the copolymer of styrene and the Parts aforementioned unsaturated dioxolane. Sodium lauryl sulfate 1.5 The copolymer latex may be used as a coating Ammonium persulfate 0.5

composition or a component of such composi- Deionized water 300.0

- The resulting-- mixture 13 is heated with stirring in a reaction vessel placed on a steam bath for 1% hours, after which stirring is stopped, and steam is passed rapidly through the mass for 15 minutes in order to remove unreacted monomers.

The steamed emulsion is cooled and strained to remove lumps of coagulated copolymer. A portion of the emulsion is diluted with water to 10% solids and is used to impregnate woolen fabrics.

The impregnated cloth is dried for 10 minutes" Example 15 Parts 2,5-dichlorostyrene 300 4-allyl-1,3-dioxolane 100 Benzoyl per 2 are mixed and the monomers copolymerized by heating the mixture at 100 C. for 144 hours, yielding a solid copolymer.

Example 16 Parts Ethyl acrylate 70 4-vinyl-2-phenyl-1,3-dioxolane 30 Benzene 100 Benzoyl per 1 are heated together under reflux at the boiling temperature of the mass for 5 hours. Films dried from the resulting solution of theunsaturated dioxolane-ethyl acrylated copolymer are clear and tough.

Similar results are obtained by substituting 30 parts of 4-al1yloxymethy1-2-phenyl-1,3-dioxolane for 30 parts of 4-vinyl-2-phenyl-L3-dioxolane in the above formula.

Example 17 Parts Styrene 180 Triallyl cyanurate 4-vinyl-2-phenyl-1,3-dioxolane 10 Benzoyl peroxide 1 are mixed and copolymerization eflected between the monomers by heating the mixture for 60 hours at 100 C. A solid copolymer is obtained which swells but does not dissolve when immersed in toluene for several days.

14 coating composition'or as a component oi. such compositions.

Example m Parts Acrylonitrile 4 5,0 7 4-vinyl-1,3-dioxolane 50 Benzoyl peroxide 1 are mixed together and charged to a heavy-walled glass tube, which thereafter is sealed under vacuum. Copolymerization is efl'ected by heating the sealed tube in a 60 0. water bath for 48 hours.

Example 18 g Parts Methyl acrylate 45.0 Ethyl acrylate 45.0 4-allyloxymethy1-L3-dioxolane 10.0

25% solution of dioctyl sodium suliosuccinate in water 20.0 Water 380.0 0% aqueous solution oi hydrogen peroxide 1.1

The same general procedure is followed as described under Example 9. Stirring and heating under reflux are continued for 5 hours, after which the emulsion is steamed for 1 hour to remove unpolymerized monomers. The resulting product ,is a fairly stable emulsion of reactive copolymer, which may be used, for example, as a The resulting copolymer can be molded under heat and pressure to yield a wide variety of molded articles for domestic and industrial use.

' Example 20 Parts Methyl methacrylate -l 50 4-allyloxymethyl-L3-di0xoiane 50 Benzoyl peroxide 1 The same general procedure is followed as described under Example 19 with the exception that the period of heating in the 60 0. water bath is only 24 hours instead of 48 hours. A hard copolymer of methyl methacrylate and 4-allyloxymethyl-1,3-dioxolane is obtained.

Example 21 Parts Vinyl acetate 50 4-vinyl-1,3-dioxolane 50 Benzoyl peroxide 1 yield a hard copolymer when copolymerized in the same manner as described under Example 20.

Example '22 Parts Vinylidene chloride 50 4-allyl-1 ,3-dioxolane 50 Benzoyl peroxide 1 yield a moderately hard copolymer when copolymerized in the same manner as described under Example 20.

Example 23 Parts Diallyl tetrafluorosuccinate 380 Triallyl cyanurate l0 4-allyl-1,3-dioxoiane 10 Benzoyl peroxide 2 are heated together for 3 hours at C. yielding an insoluble copolymeric solid. This copolymer supports combustion less readily, that is, it burns more slowly, than polymeric (homopolymeric) diallyl succinate, and is suitable for uses, e. g., in electrically insulating applications, in making flame-resistant laminated articles, etc., for which polymeric diallyl succinate would be either wholly unsuited or would have only limited utility.

Example 24 Parts 2,5-dimethylstyrene 4-vinyl-2-phenyl-1,3-dioxolane 40 Benzoyl peroxide 1 are mixed together and charged to a heavy-walled glass tube, which thereafter is sealed under vacuum. Polymerization of the polymerizable mixture is allowed to proceed for 400 hours at room temperature (20 to 30 C.) and mentor 15 days at 60 C., yielding a hard coploymer of the unsaturated dioxolane and the 2,5-dimethylstyrene.

Example '25 Ethyl acrylate 10.0 4-vinyl-2-phenvl-L3-dioxolane 10.0 Toluene 20.0 Benzoyl peroxide 0.2

was heated together under at the boiling temperature of the mass for 5 hours. The resulting solution of copolymer contains 23.1% 01' copolymer solids, which corresponds to approximately 46 conversion of monomers to copolymer. Clear films are obtained by casting the solution on glass plates and baking at 150 C. to evaporate the toluene.

Example 26 Parts Ethyl acrylate 10.0 4-allyloxymethyl-L3-dioxolane 10.0 Toluene 20.0 Benzoyl peroxide .4 0.2

The same procedure is followed as described under Example 25. The yield of copolymer solids .is 28.6% which corresponds to 57.2% conversion of monomers to copolymer. Clear films are obtained by casting the solution on glass plates and baking as described in the preceding example.

Example 27 Parts 4-allyloxymethyl-l;3-dioxolane 10.0 Styrene 10.0 Xylene 20.0 2,2-bis(di-tert.-butyl peroxy) butane 0.2

\ Example 28 Parts 4-vinyl-1,3-dioxolane 40.0 Ethyl acrylate 1 54.0 Styrene 26.0 Xylene 120.0 2,2-bis(di-tert.-butyl peroxy) butane 1.2

are heated together under reflux as described under Example 27, yielding a viscous solution of the unsaturated dioxolane-ethyl acrylate-styrene copolymer. Films produced by dryin this solution are clear and tough, and they can be made more solvent-resistant by adding to the solution, prior to drying, a small amount of tetraethylenepentamine, ethylene diamine or other polyamine.

Example 29 Parts Acrylonitrile 100.0 4-allyloxymethyl-l,3-dioxolane 100.0 25 solution of dioctyl sodium sulfosuccinate 24.4 Water I 574.0 30% aqueous solution of hydrogen peroxide 4.4

All of the above ingredients with the exception of one-half (2.2 parts) of the aqueous hydrogen peroxide solution are charged to a reaction vessel as described under Example 9. The mixture is stirred vigorously while heating under reflux on a steam bath for 1% hours, after which the refiltered to isolate the copolymer. The filter cake of copolymer is washed with water and dried in a vacuum oven at 50 C. for 48 hours, yielding a dried, reactive copolymer of acrylonitrile and 4- allyloxymethyl-l,3-dioxolane. This reactive copolymer, alone or admixed with a filler, polymerization catalyst or other additive, is adapted to be molded under heat and pressure to yield molded articles of various shapes.

Example Parts 4-allyloxymethyl-1,3-dioxolane 20 Benzoyl peroxide 1 are mixed together and charged to a heavy-walled glass tube, which thereafter is sealed under vacuum and then placed in a 120 C. oven for 5 days. A viscous polymer of 4-allyloxymethyl-1,3- dioxolane is obtained at the end of the polymerization period. When a small amount, e. g., 2-5% by weight, of anhydrous stannic chloride is added to the viscous polymer at 20-30 C., a gel forms upon contact of the catalyst with the polymer, indicating that the linear liquid polymer (wherein polymerization has taken place primarily through the ethylenic linkage) has been cross-linked through rupture of the dioxolane ring.

Example 31 Parts 4-vinyl-2-phenyl-11,3-dioxolane 20 j Stannic chloride (anhydrous) 1 are mixed together at room temperature, whereupon a protion of the mass sets to a gel. Upon heating the mixture of gel and liquid phase for a prolonged period at an elevated temperature,

e. g., for 17 hours at 0., the entire mass is converted into a hard, resinous solid.

Example 32 l 1 Parts 4-vinyl-1,3-dioxolane 20 Stannic chloride (anhydrous) 1 are mixed together at room temperature whereupon a slightly viscous syrup is ohtained. This syrupy polymer is capable of undergoing further reaction, as shown by the fact that it is converted into a hard resin when heated as described under Example 31.

Example 33 Parts 4-allyloxymethyl-1,3-diox0lane 20 Stannic chloride (anhydrous) 1 are mixed together as described under Examples 31 and 32. A soft gel is formed on first contact of the catalyst with the monomer.

Example 34 17 Examples 31-34 illustrate the use of a strongly acid catalyst in eflfecting polymerization of the unsaturated dioxolanes of this invention. The following example illustrates the use of a basic catalyst.

Example 35 Parts 4-vinyl-1,3-dioxolane 20 Tetraethylenepentamine 1 are mixed together at 20-30 C. (room temperature), whereupon an exothermic reaction occurs and the entire mass is converted to a gummy polymer. This polymer is capable of undergoing further reaction as evidenced by the fact that. when it is heated for 17 hours at 120 C. it is converted into a solid resin.-

It will be understood, of course, by those skilled in the art that our invention is not limited to the specific ingredients named in the above illustrative examples nor to the particular proportions and methods of polymerization and copolymerization mentioned therein. Thus, instead of benzoyl peroxide and the other catalysts named in the difierent examples, any other polymerization catalyst or combination of polymerization catalysts, numerous examples of which have been given hereinbefore, may be used. Other catalysts that can be employed are other salts of per-acids, e. g., sodium and potassium persulfates, sodium and potassium percarbonates, sodium and potassium perborates, sodium and potassium perphosphates, etc. Also, instead of using the un saturated dioxolane and the other comonomer or comonomers in the particular proportions given in the various examples, they can be used in any other proportions, as desired or as conditions may require, for instance in the proportions mentioned by way of illustration in the portion of the specification prior to the examples, and also under Example 6 with particular reference to acrylate comonomers.

A comonomer (or plurality of comonomers) which contains one or more CH2=C groupings,-

which isdiflerent from the unsaturated dioxolane and which is compatible and copolymerizable therewith, other than the particular comonomers given in the above illustrative examples, also can be used. For instance, the comonomer may be a cyanoalkyl ester of an acrylic acid, e. g., mono-, diand tricyanomethyl esters of acrylic acid, methacrylic acid, etc., the mono-, diand tri-(fl-cyanoethyl) esters of acrylic acid, methacrylic acid, etc. Or, the comonomer can be any other organic compound which is copolymerizable with the unsaturated dioxolane and which is represented by the general formula IX B.

where R represents a member of the class consisting of hydrogen, halogen (chlorine, fluorine, bromine or iodine), alkyl (e. g., methyl, ethyl, propyl, butyl to octadecyl, inclusive), including cycloalkyl (e. g., cyclohexyl, etc.), aryl (e. g., phenyl, xenyl, naphthyl, etc.) alkaryl (e. g., tolyl, xylyl, ethylphenyl, etc.), aralkyl (e. g., benzyl, phenylethyl, etc.) and R represents an aryl radical or a radical represented by the formula ins" where R" represents an alkyl, alkoxyalkyl (e. g., methoxymethyl, methoxyethyl, ethoxyethyl, ethoxypropyl, propoxybutyl, etc.) or a carbocyclic radical (e. g., aryl, alkaryl, hydroaromatic, etc.). Examples of compounds embraced by Formula IX are the vinyl esters (e. g., vinyl acetate, etc.), methyl vinyl ketone, isoprene, 1,3-butadiene, 2- chloro-L3-butadiene, acrylonitrile, various esters of acrylic acid (e. 8., methyl acrylate, ethyl acrylate, cyclohexyl acrylate, tetrahydronaphthyl acrylate, decahydronaphthyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, etc.) as well .as others that will be obvious to those skilled in the art.

The thermosetting or potentially thermosetting, reactive polymerization products (polymers and copolymers) of this invention have a wide variety of applications. For instance, with or without a filler or other additive, numerous examples of which have been given hereinbefore, they may be used as molding compositions (or as components of molding compositions) 'from which molded articles are produced by molding the composition under heat and pressure, e. g., at temperatures of the order of to 200 C. and under pressures ranging between 1000 and 10,000 pounds per square inch. Among the fillers that can be employed in the production of molding compositions are alpha-cellulose pulp, asbestos fibers, cotton flock, chopped cloth cuttings, glass fibers, wood flour, antimony oxide, titanium diotxide, sand, clay, mica dust, diatomaceous earth, e c.

The liquid polymerizable compositions of our invention also can be used in the production of castings; as adhesives, for instance in the production of optical devices containing a plurality of elements, examples of which are compound lenses, compound prisms, Nicol prisms, etc.; in

the treatment of paper or paper stock; and for various other purposes.

We claim:

1. A compound represented by the general formula where R represents an allyloxymethyl radical, and R represents an aryl radical.

2. A polymer of a monomer represented by the general formula where R represents an allyloxymethyl radical, and R represents an aryl radical.

3. A polymerizable composition comprising (1) a compound represented by the general formula R-on cm where R represents an allyloxymethyl radical, and R represents an aryl radical, and (2) a compound which is different from the compound 19 of (1), is copolymerizable therewith and which contains a CH2=C grouping.

4. A polymerlzable composition as in claim 3 wherein the compound of (2) is a vinyl compound.

5. A composition comprising a coplymer of copolymerizable ingredients including compound represented by the general formula 9. A composition as in claim 8 wherein the vinyl aromatic hydrocarbon is styrene.

10. A composition as in claim 21 wherein the vinyl aliphatic compound is acrylonitrile.

11.-A composition as in claim 21 wherein the vinyl aliphatic compound is an alkyl ester of acrylic acid.

12. The method of preparing a new synthetic composition which comprises polymerizing under heat, while admixed with a polymerization catalyst, a compound represented by the general formula R-C 11-0 H:

where R repersents an allyloxymethyl radical, and R represents an aryl radical.

13. The method of preparing a new synthetic composition which comprises polymerizing under heat, while admixed with a polymerization catalyst, a polymerizable composition comprising a compound represented by the general formula R-cn cn,

CER' where R represents an allyloxymethyl radical, and R represents an aryl radical, and (2) a compound which is different from the compound 2o of (1), is copolymerizable therewith and which contains a CH2=C grouping.

l4. 4-allyloxymethyl-2-phenyl-1,3-dioxolane.

15. A polymer of 4-allyloxymethyl-2-phenyl- 1,3-dioxolane.

16. A homopolymer of 4-allyloxymethyl-2- phenyl-LS-dioxolane.

17. A composition comprising a copolymer of copolymerizable ingredients including (1) 4- allyloxymethyl-2-phenyl-1,3-dioxolane and (2) a compound which is different from the compound of (1), is copolymerizable therewith and contains a CHa=C grouping.

18. A composition comprising a copolymer of copolymerizable ingredients including 4-allyloxymethyl-Z-phenyl 1,3 dioxolane and. ethyl acrylate.

19. A copolymer of a mixture of monomers consisting of, by weight, 70 parts of ethyl acrylate and 30 parts of 4-allyloxymethyl-2-phenyl-1,3- dioxolane.

20. A benzene solution of a soluble copolymer of a mixture of monomers consisting of, by weight,

70 parts of ethyl acrylate and 30 parts of 4- allyloxymethyl-2-phenyl-1,3-dioxolane.

21. A composition comprising a copolymer of copolymerizable ingredients including (1) a compound represented by the general formula n-cm-cm where R. represents an allyloxymethyl radical, and R represents an aryl radical, and (2) a vinyl aliphatic compound which is copolymerizable with the compound of (1).

WALTER M. THOMAS. EDWARD L. KROPA.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS OTHER REFERENCES Chem. Abst., vol. 40, page 6467 (1946). Chem. Abst., vol. 42, page 4944 (1948). 

1. A COMPOUND REPRESENTED BY THE GENERAL FORMULA 